Catalyst – solid sorbent – or support therefor: product or process – Catalyst or precursor therefor – Sulfur or compound containing same
Reexamination Certificate
2001-04-10
2004-06-22
Bell, Mark L. (Department: 1755)
Catalyst, solid sorbent, or support therefor: product or process
Catalyst or precursor therefor
Sulfur or compound containing same
C502S219000, C502S220000, C502S221000, C502S222000, C502S313000
Reexamination Certificate
active
06753291
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a process for sulfiding organic additive-containing catalysts, in particular organic additive-containing hydrotreating catalysts.
2. Description of the Prior Art
Hydrotreating catalysts comprise hydrogenation metal components, generally a Group VI metal component such as molybdenum and/or tungsten and a Group VIII metal component, such as nickel and/or cobalt generally on an oxidic carrier.
Organic additive-containing hydrotreating catalysts are known in the art. For example, European patent application 0 601 722 describes hydrotreating catalysts comprising a gamma-alumina support impregnated with a Group VIB metal component, a Group VIII metal component, and an organic additive which is at least one compound selected from the group of compounds comprising at least two hydroxyl groups and 2-10 carbon atoms, and the ethers and polyethers of these compounds.
Japanese patent application 04-166231 describes a hydrotreating catalyst prepared by a process in which a support is impregnated with an impregnation solution comprising a Group VIB metal component, a Group VIII metal component, and, optionally, a phosphorus component. The support is dried at a temperature below 200° C., contacted with a polyol, and then dried again at a temperature below 200° C. Japanese patent application 04-166233 describes an alkoxycarboxylic acid-containing catalyst prepared by substantially the same process.
Japanese patent application 06-339635 describes a hydrotreating catalyst prepared by a process in which a support is impregnated with an impregnation solution comprising an organic acid, Group VIB and Group VIII hydrogenation metal components, and preferably a phosphorus component. The impregnated support is dried at a temperature below 200° C. The dried impregnated support is contacted with an organic acid or polyol, after which the thus treated support is dried at a temperature below 200° C.
Japanese patent application 06-210182 describes an additive-containing catalyst based on a boria-alumina support comprising 3-15 wt. % of boria. Non-prepublished European patent application No. 99201051.2 in the name of Akzo Nobel filed on Apr. 8, 1999, describes a catalyst containing an organic compound comprising N and carbonyl.
The additive-containing catalysts of the above references all show an increased activity in the hydrotreating of hydrocarbon feeds as compared to comparable catalysts which do not contain an organic additive.
Before use, the hydrogenation metal components present in hydrotreating catalysts, including the additive-containing catalysts of the above references, will generally be converted into their sulfides. This process is conventionally indicated as sulfidation or presulfidation. It is generally done before the catalyst is used in hydrotreating to ensure a stable reactor performance.
The above-mentioned references indicate that the catalysts described therein can suitably be sulfided in the hydrotreating reactor by being contacted in the liquid phase with a sulfur-containing hydrocarbon feed in the presence of hydrogen. This can either be a feed to which a sulfur component, e.g., dimethyldisulfide, has been added (spiked feed) or, if the sulfur content of the feed to be hydrotreated is sufficiently high, the feed itself.
However, not all hydrotreating units are suitable for such in situ liquid sulfidation procedures. Some hydrotreating units use a gas phase sulfiding process, conventionally with H
2
S and H
2
or with H
2
and a compound which decomposes into H
2
S, such as DMDS.
Moreover, some hydrotreating units are required by the authorities to carry out a pressure test as part of their start-up procedure. This pressure test is generally carried out in the presence of hydrogen at a pressure above operating pressure and a temperature above 100° C. in the absence of liquid.
It has been found that when an additive-containing catalyst is subjected to a gas phase start-up procedure or a start-up procedure including a pressure test, the activity of the catalyst is not good.
There is therefore need for a process for sulfiding additive-containing catalysts which would make it possible to obtain catalysts suitable for units which cannot perform sulfidation in the liquid phase or which are required to carry out a pressure test as described above.
SUMMARY OF THE INVENTION
In one embodiment, our invention is the obtaining of sulfided catalysts with a high activity by way of a gas phase sulfidation process in which a catalyst composition comprising at least one hydrogenation metal component of Group VI and/or Group VIII of the Periodic Table and an organic additive is first contacted with an organic liquid, followed by the catalyst being contacted with hydrogen and a sulfur-containing compound in the gaseous phase, wherein less than 40% of the sulfur present in the sulfided catalyst is added with the organic liquid.
In a second embodiment, our invention is a catalyst obtained by the above process.
In a third embodiment, our invention is a process for hydrotreating a hydrocarbon feed by contacting the feed with the above catalyst at hydrotreating conditions.
Other embodiments of our invention encompass details about reactant compositions, process steps and conditions, etc., all of which are hereinafter disclosed in the following discussion of each of the facets of our invention.
DETAILED DESCRIPTION OF THE INVENTION
The Sulfidation Process
In the process according to the invention, the organic additive-containing catalyst is first contacted with an organic liquid. The organic liquid generally has a boiling range of about 100-550° C., preferably about 150-500° C. It generally is a petroleum fraction. By their nature, petroleum fractions comprise less than about 12 wt. % of oxygen. Petroleum fractions comprising less than about 8 wt. % of oxygen, preferably less than about 5 wt. %, more preferably less than about 2 wt. %, specifically less than about 0.5 wt. % of oxygen, may be preferred. Although the olefin content of the organic liquid is not critical to the process according to the invention, petroleum fractions with and iodine number of about 50 or less, specifically about 30 or less, may be preferred. Examples of suitable petroleum fractions include fractions comprising heavy oils, lubricating oil fractions like mineral lube oil (360° C.<BP<500° C.), atmospheric gas oils, vacuum gas oils, straight run gas oils (250° C.<BP<350° C.), white spirit (180° C.<BP<220° C.), middle distillates like diesel, jet fuel and heating oil, naphthas, and gasoline. Preferably white oil, gasoline, diesel, gas oil, or mineral lube oil is used.
The organic liquid ensures that the catalyst is able to withstand the conditions prevailing during the actual sulfidation step, that is, during the contacting of the catalyst with hydrogen and a sulfur-containing compound, or during the pressure test. The organic liquid is not particularly intended to bring sulfur into the catalyst. Nevertheless, petroleum cuts such as a gas oil or diesel may sometimes contain sulfur. Generally, the organic liquid will contain less than about 10 wt. % of sulfur, preferably less than about 5 wt. %. The amount of sulfur added with the organic liquid will be less than about 40%, preferably less than about 35% of the total amount of sulfur added to the catalyst with the organic liquid and by way of the sulfur-containing compound applied in the gaseous phase, more preferably less than about 25%, even more preferably less than about 15%.
The amount of organic liquid generally is about 20-500% of the catalyst pore volume which can be filled with the liquid at issue under the conditions of application of the liquid. The pore volume can easily be determined by slowly adding liquid under said conditions to a certain amount of catalyst in a closed flask while shaking and determining by visual inspection when the liquid is no longer adsorbed. Another method is to add excess liquid and to remove the excess from the catalyst, e.g., by centrifugati
Dufresne Pierre
Eijsbouts Sonja
Gerritsen Leendert Arie
Labruyere Franck
Plantenga Frans Lodewijk
Akzo Nobel N.V.
Bell Mark L.
Hailey Patricia L.
Morris Louis A.
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